Azo dyestuffs having a carboxyl group and an iminosulfonamido, iminosulfonylalkyl or iminosulfonylaryl group in the coupling component

ABSTRACT

Dyestuffs of the formula ##STR1## wherein D is a diazo component of the benzene series, 
     R 1  is an alkyl radical, 
     R 2  is alkylene and 
     R is alkyl, aryl or di-substituted amino, dye polyester fibers in red and blue shades with good fastness. The dyestuffs can be used in the thermosol process.

This is a continuation of application Ser. No. 485,054, filed July 1,1974 (now abandoned), which in turn, was a continuation of ApplicationSer. No. 243,469 filed Apr. 12, 1972, now abandoned.

The present invention relates to valuable, new azo compounds which arefree from sulphonic acid and have the formula ##STR2## wherein D is theradical of a diazo component, R₁ is a hydrogen atom or an optionallysubstituted alkyl radical, R₂ represents an optionally substitutedarylene radical or preferably an optionally substituted alkyleneradical, R is an optionally substituted alkyl or aryl radical or aradical of the formula ##STR3## wherein R₃ and R₄ are each alkyl groupsor together with the nitrogen atom form a 5- or 6-membered ring which isoptionally interrupted by a hetero atom, and d is a hydrogen atom, achlorine atom, a lower alkyl, alkoxy radical or an aryl, aryloxy orarylmercapto radical, and the radical of the coupling component to theright of the --N═N--group contains only one group of the formula--CO--OR₅, wherein R₅ is a hydrogen atom or an alkyl radical.

According to the invention, the compounds are obtained by coupling adiazonium compound of a diazo component with a coupling component of theformula ##STR4##

Interesting dyestuffs are those of the formula ##STR5## and those of theformula ##STR6##d wherein R' is a lower alkyl group.

The radical d preferably represents a hydrogen atom, a lower alkyl oralkoxy radical, such as the methyl, ethyl, methoxy or ethoxy radical,also a phenyl, phenylthio or phenoxy radical.

The group R₁ represents a hydrogen atom or a lower alkyl group (i.e.,containing from 1 to 4 carbon atoms), such as methyl, ethyl, propyl orbutyl groups, or a substituted alkyl group i.e., substituted methyl,ethyl, n-propyl, isopropyl or butyl groups, for example phenylalkylgroups, such as benzyl or β-phenylethyl groups halogenated alkyl groups,such as β-chloroethyl β,β,β-trifluoroethyl and β,γ-dichloropropylgroups, and β-cyanoethyl groups; cyanoethoxyethyl; β-hydroxyethyl-;alkoxyalkyl-, such as β-ethoxyethyl-, δ-methoxybutyl- or δ-butoxybutyl;acylaminoalkyl groups, such as β-(acetyl- or formyl)-aminoethyl,benzoylaminoethyl or dodecylcarbonylaminoethyl groups; acyloxyalkylgroups, such as β-formyloxyethyl, β-acetyloxyethyl, β,γ-diacetoxypropyl,γ-butyryloxypropyl, benzoyloxybutyl, decylcarbonyloxyethyl,dodecylcarbonyloxyethyl and their chlorinated or brominated C₁ -C₅derivatives, such as chloroacetyloxyethyl andα,β-dibromopropionyloxyethyl groups; β-arylsulphonylalkyl groups, suchas β-phenylsulphonylethyl, β-(p-toluenesulphonyl)-ethyl orβ-(p-chlorobenzenesulphonyl)-ethyl, β-(p-toluenesulphonyl)-ethyl groups;alkyl or arylcarbamoyloxyalkyl groups, such as β-methylcarbamyloxyethyl,butylcarbamyloxy, dodecylcarbamyloxy and β-(methoxy, ethoxy orisopropyloxy)-carbonyloxethyl, aryloxycarbonyloxy, such asphenoxycarbonyloxy, β-(p-hydroxyphenoxy)-ethyl, β-phenoxyethyl,β-toluyloxyethyl, β-acetylethyl, β-cyanoacetoxyethyl, and β-(p-alkoxy-or phenoxybenzoyl)-oxyethyl groups; The groups R₁ and R₂ contain ingeneral not more than 18, but preferably not more than 10 carbon atoms.

The radical R₂ is an optionally substituted phenylene radical orpreferably a straight-chain or branched alkylene group containing from 1to 4 carbon atoms, for example one of the radicals ##STR7##

Of the optional diazotisable amines which are free fromwater-solubilising groups and are suitable as the diazo component D-NH₂,special mention may be made of those amines which have a heterocyclic5-membered ring containing 2 or 3 hetero atoms, primarily a nitrogenatom and one or two sulphur, oxygen or nitrogen atoms as hetero atoms,as well as aminobenzenes.

Preferred heterocyclic diazo components belong to the series of thethiazoles, benzthiazoles, isothiazoles, benzisothiazoles,1,3,4-thiadiazoles, 1,3,5-thiadiazoles, pyrazoles, indazoles, pyridinesor thiophenes.

Preferably D represents a phenyl radical which is optionally substitutedby chlorine or bromine atoms, hydroxyl, cyano, thiocyanogen-, nitro,methyl, ethyl, trifluoromethyl, methoxy, ethoxy, formyl, acetyl,propionyl, benzoyl, methylbenzoyl, methoxycarbonyl, ethoxycarbonyl,ethoxycarbonyloxy, benzyloxycarbonyloxy, acetoxy, propionyloxy,benzoyloxy, methoxyethoxycarbonyl, acetylamino, propionylamino,benzoylamino, methoxycarbonylamino, ethoxycarbonylamino,methylsulphonyl, ethylsulphonyl, propylsulphonyl, butylsulphonyl,chloromethylsulphonyl-, aminosulphonyl, methylaminosulphonyl,dimethylaminosulphonyl, di-(hydroxyethyl)-aminosulphonyl,cyclohexylaminosulphonyl, phenylaminosulphonyl,chlorophenylaminosulphonyl, methoxyphenylaminosulphonyl,benzylaminosulphonyl, N-piperidylsulphonyl-, N-morpholinosulphonyl,methylsulphonyloxy, ethylsulphonyloxy, ethoxyethylsulphonyloxy,propylsulphonyloxy, hexylsulphonyloxy, cyclohexylsulphonyloxy,chloromethylsulphonyloxy, cyanoethylsulphonyloxy, phenylsulphonyloxy,chlorophenylsulphonyloxy, aminosulphonyloxy, N-morpholinosulphonyloxy-,methoxyphenylsulphonyloxy, ethyleneiminosulphonyloxy,methylaminosulphonyloxy, ethylaminosulphonyloxy,propylaminosulphonyloxy, butylaminosulphonyloxy,dimethylaminosulphonyloxy, diethylaminosulphonyloxy,dipropylaminosulphonyloxy, dibutylaminosulphonyloxy,phenylaminosulphonyloxy, N-phenyl-N-methylaminosulphonyloxy,N-phenyl-N-ethylaminosulphonyloxy, methoxyphenylaminosulphonyloxy,phenylamino, nitrophenylamino, dinitrophenylamino, phenyl-,acetylaminophenyl, phenylaminosulphonylphenyl, phenylazo ornitrophenylazo groups, a naphthyl radical which is optionallysubstituted by methoxy, ethoxy, phenylazo or dimethylaminosulphonylgroups, a thiazolyl radical which is optionally substituted by chlorineor bromine atoms, nitro, cyano, thiocyano, lower alkyl, lower aralkyl,phenyl, lower cyanoalkyl, lower alkoxy, lower alkoxycarbonyl,trifluoromethyl, lower alkylcarbonyl or lower alkylsulphonyl groups, abenzthiazole radical which is optionally substituted by chlorine orbromine atoms, cyano, thiocyano, lower alkyl, lower alkoxy, loweraraloxy, phenyl, lower alkylmercapto, lower alkylsulphonyl,trifluoromethyl, nitro, cyanoethylsulphonyl, optionally, mono- anddialkylated aminosulphonyl or lower alkoxycarbonyl groups, a pyrazolylradical which is optionally substituted by cyano, lower alkyl, loweralkoxy, lower alkoxycarbonyl or phenyl groups, a thiadiazolyl radicalwhich is optionally substituted by chlorine or bromine atoms, loweralkoxy, alkylmercapto, lower alkyl, lower alkylsulphonyl, phenyl,methylthiophenyl, nitrophenyl, tolyl, chlorophenyl or bromophenylgroups, an imidazolyl radical which is optionally substituted by nitroor lower alkyl groups, a thienyl radical which is optionally substitutedby nitro, lower alkoxycarbonyl, lower alkyl, lower alkylsulphonyl,acetyl or optionally alkylated aminosulphonyl groups, an isothiazolylradical which is optionally substituted by alkyl, phenyl or cyano,groups, a benzisothiazolyl radical which is optionally substituted bylower alkyl or nitro groups or bromine or chlorine atoms, or a pyridineradical which is substituted by lower alkyl groups, cyano groups,bromine or chlorine atoms.

A valuable selection of diazo components is also represented by thenegatively substituted aminobenzenes, for example those of the formula##STR8## wherein a represents a hydrogen for halogen atom, an alkyl oralkoxy, nitro, cyano, carbaloxy or alkylsulphonyl group, b represents ahydrogen or halogen atom, an alkyl, cyano or alkylsulphonyl group.

Negatively substituted anilines are those which contain negativesubstituents, i.e., substituents which intensify the acid properties ofphenol or possess a positive sigma value (Hammet).

As examples there may be cited:

2-aminothiazole,

2-amino-5-nitrothiazole,

2-amino-5-methylsulphonyl-thiazole,

2-amino-5-cyanothiazole,

2-amino-4-methyl-5-nitrothiazole,

2-amino-4-methylthiazole,

2-amino-4-phenylthiazole,

2-amino-4-(4'-chloro)-phenylthiazole,

2-amino-4-(4'-nitro)-phenylthiazole,

3-aminopyridine,

3-aminoquinoline,

3-aminopyrazole,

3-amino-1-phenylpyrazole,

3-aminoindazole,

3-amino-1,2,4-triazole,

5-(methyl-, ethyl-, phenyl- or benzyl)-1,2,4-triazole,

3-amino-1-(4'-methoxyphenyl)-pyrazole,

2-aminobenzthiazole,

2-amino-6-methylbenzthiazole,

2-amino-6-methoxybenzthiazole,

2-amino-6-chlorobenzthiazole,

2-amino-6-cyanobenzthiazole,

2-amino-6-thiocyanobenzthiazole,

2-amino-6-nitrobenzthiazole,

2-amino-6-carboethoxybenzthiazole,

2-amino-(4- or 6)-methylsulphonylbenzthiazole,

2-amino-1,3,4-thiadiazole

2-amino-1,3,5-thiadiazole, 2-amino-4-phenyl- or-4-methyl-1,3,5-thiadiazole,

2-amino-5-phenyl-1,3,4-thiadiazole,

2-amino-3-nitro-5-methylsulphonyl-thiophene,

2-amino-3,5-bis-(methylsulphonyl)-thiophene,

5-amino-3-methyl-isothiazole,

2-amino-4cyano-pyrazole,

2-(4'-nitrophenyl)-3-amino-4-cyanopyrazole,

3- or 4-aminophthalimide,

aminobenzene,

1-amino-4-chlorobenzene,

1-amino-4-bromobenzene,

1-amino-4-methylbenzene,

1-amino-4-nitrobenzene,

1-amino-4-cyanobenzene,

1-amino-2,5-dicyanobenzene,

1-amino-4-methylsulphonylbenzene,

1-amino-4-carbalkoxybenzene,

1-amino-2,4-dichlorobenzene,

1-amino-2,4-dibromobenzene,

1-amino-2-methyl-4-chlorobenzene,

1-amino-2-trifluoromethyl-4-chlorobenzene,

1-amino-2-cyano-4-chlorobenzene,

1-amino-2-carbomethoxy-4-chlorobenzene,

1-amino-2-carbomethoxy-4-nitrobenzene,

1-amino-2-chloro-4-cyanobenzene

1-amino-2-chloro-4-nitrobenzene,

1-amino-2-bromo-4-nitrobenzene,

1-amino-2-chloro-4-carboethoxybenzene,

1-amino-2-chloro-4-methylsulphonylbenzene,

1-amino-2-methylsulphonyl-4-chlorobenzene,

1-amino-2,4-dinitro-6-methylsulphonylbenzene,

1-amino-2,4-dinitro-6-(2'-hydroxyethylsulphonyl)-benzene,

1-amino-2,4-dinitro-6-(2'-chloroethylsulphonyl)-benzene,

1-amino-2-methylsulphonyl-4-nitrobenzene,

1-amino-2-methylsulphinyl-4-nitrobenzene,

1-amino-2,4-dinitrobenzene,

1-amino-2,4-dicyanobenzene,

1-amino-2-cyano-4-methylsulphonylbenzene,

1-amino-2,6-dichloro-4-cyanobenzene,

1-amino-2,6-dichloro-4-nitrobenzene,

1-amino-2,4-dicyano-6-chlorobenzene,

4-aminobenzoic acid cyclohexyl ester,

1-amino-2,4-dinitro-6-chlorobenzene and in particular

1-amino-2-cyano-4-nitrobenzene,

1-aminobenzene-2, -3- or -4-sulphonic acid amides, for example

N-methyl- or N,N-dimethyl- or -diethylamide,

N,γ-isopropyloxypropyl-2-amino-naphthalene-6-sulphonic acid amide,

N,γ-isopropyloxypropyl-1-aminobenzene-2, -3- or -4-sulphonic acid amide,

N-isopropyl-1-aminobenzene-2-, -3- or -4-sulphonic acid amide

N,γ-methoxypropyl-1-aminobenzene-2-, -3- or -4-sulphonic acid amide,

N,n-bis-(β-hydroxyethyl)-1-aminobenzene-2-, -3- or -4-sulphonic acidamide,

1-amino-4-chlorobenzene-2-sulphonic acid amide,

and the N-substituted derivatives,

2-, 3- or 4-aminophenylsulphamate,

2-amino-4, -5- or -6-methylphenylsulphamate,

2-amino-5-methoxy-phenylsulphamate,

3-amino-6-chlorophenylsulphamate,

3-amino-2,6-dichlorophenylsulphamate,

4-amino-2- or -3-methoxyphenylsulphamate,

N,n-dimethyl-2-aminophenylsulphamate,

N,n-di-n-butyl-2-aminophenylsulphamate,

N,N-dimethyl-2-amino-4-chlorophenylsulphamate,

N,n-propyl-2-aminophenylsulphamate,

N,N-di-n-butyl-3-aminophenylsulphamate,

O(3-aminophenyl)-N-morpholine-N-sulphonate,

O(3-aminophenyl)-N-piperidine-sulphonate, N-cyclohexyl-O-(3-aminophenyl)-sulphamate,

N(n-methylaniline)-O-( 3-aminophenyl)-sulphonate,

N,n-diethyl-3-amino-6-methylphenyl-sulphamate,

N-ethyleneimine-O-( 4-aminophenyl)-sulphonate,

N,n-dimethyl-4-aminophenylsulphamate,

O(n-propyl)-O-( 3-aminophenyl)-sulphonate,

O,β-chloroethyl-O-(2-aminophenyl)-sulphonate,

O-benzyl-O-(3-aminophenyl)-sulphonate and

O-ethyl-O-(4-amino-2,6-dimethyl-phenyl)-sulphonate.

Examples of

4-aminobenzenes which may be used as diazo components are:

4-aminoazobenzene,

3,2-dimethyl-4-aminoazobenzene,

2-methyl-5-methoxy-4-aminoazobenzene,

4-amino-2-nitroazobenzene,

2,5-dimethoxy-4-aminoazobenzene,

4'-methoxy-4-aminoazobenzene,

2-methyl-4'-methoxy-4-aminoazobenzene,

3,6,4'-trimethoxy-4-aminoazobenzene,

4'-chloro-4-aminoazobenzene,

2'- or 3'-chloro-4-aminoazobenzene,

3-nitro-4-amino-2',4'-dichloroazobenzene and

4-aminoazobenzene-4'-sulphonic acid amide.

Instead of the above cited diazo components that are free from ionogenicwater-solubilising groups, it is also possible to use those that containfibre reactive groups such, for example, as s-triazinyl radicals thatcarry 1 or 2 chlorine or bromine atoms on the triazine ring, pyrimidylradicals that carry 1 or 2 arylsulphonyl or alkanesulphonyl groups onthe pyrimidine ring, mono-, or bis-(γ-halogeno-β-hydroxypropyl)-aminogroups, β-halogeno-ethylsulphamyl radicals, β-halogeno-ethoxy groups,β-halogeno-ethylmercapto groups, 2-chloro-benzthiazolyl-6-azo groups,2-chlorobenzthiazolyl-6-amino groups,γ-halogeno-β-hydroxy-propylsulphamyl radicals, chloroacetylamino groups,α,β-dibromopropionyl groups, vinylsulphonyl groups and 2,3-epoxypropylgroups.

Suitable fibre reactive diazo components are, for example:

N,β-chloroethyl-3-chloro-4-amino-benzenesulphamide (hydrochloride),

N,β-chloroethyl-4-aminobenzene-sulphamide (hydrochloride)

3-bromo-4-amino-ωchloroacetophenone,

N,γ-chloro-β-hydroxypropyl-4-aminobenzene-sulphamide,

N,β-chloroethyl-1-amino-4-naphthylsulphonamide,

N,β-chloroethyl-1-amino-3,5-dichloro-benzenesulphamide and

4-(γ-chloro-β-hydroxy-propoxy) aniline.

The compounds manufactured with such diazo components contain instead ofthe fibre-reactive acylamino group Ac, which is present according to theinvention, an additional fibre-reactive group whose reactivity may begreater or lesser than that of the group Ac.

The diazotisation of the cited diazo components can take place in knownmanner, for example with the aid of mineral acid and sodium nitrite or,for example, with a solution of nitrosylsulphuric acid in concentratedsulphuric acid.

The coupling can likewise be carried out in known manner, for example inneutral to acid medium, optionally in the presence of sodium acetate orsimilar buffer substances or catalysts that influence the couplingspeed, for example dimethylformamide, pyridine or its salts.

The coupling components can be manufactured as follows:

1. Coupling component of the type having the formula ##STR9##

The coupling components are obtained by reacting a3-alkylsulphonylaminoaniline with acrylic acid or with aω-halogenocarboxylic acid, for example β-bromopropionic acid orchloroacetic acid.

To manufacture the 3-alkylsulphonylaminoanilines, m-nitroaniline isacylated with one of the sulphonic acids or halides thereof listedhereunder, and the nitro group is reduced with iron/hydrochloric acid orcatalytically with Raney nickel to the amino group.

Suitable sulphonic acids of the formula R-SO₃ H are:

methanesulphonic acid

ethanesulphonic acid

n-propanesulphonic acid

n-butanesulphonic acid

isopentanesulphonic acid

allylsulphonic acid

vinylsulphonic acid

β-methallylsulphonic acid

β-methoxyethanesulphonic acid

β-ethoxyethanesulphonic acid

β-butoxyethanesulphonic acid

chloro- or bromomethanesulphonic acid

α-chlorovinylsulphonic acid

benzenesulphonic acid

p-toluenesulphonic acid

p-chlorosulphonic acid

and benzylsulphonic acid.

The sulphonic acids may be used in the form of their chlorides orbromides for the acylation.

2. The coupling component of the type having the formula ##STR10## isobtained by reacting m-nitro-aniline with dialkylaminosulphonicchlorides, hydrogenating the nitro group and introducing the carboxylgroup as described hereinabove. Suitable sulpho chlorides are those ofthe formula ##STR11##

If the coupling components described above under 1) or 2) are monovalentorganic acids, they contain only one N-alkyl-CO-O group; if they aredivalent acids, they contain two N-alkyl-CO-O groups.

The new compounds, their mixtures with one another and their mixtureswith other azo dyestuffs are outstandingly suitable for dyeing andprinting leather, wool, silk and above all synthetic fibres, forexample, acrylic or acrylonitrile fibres of polyacrylonitrile or ofcopolymers, of acrylonitrile and other vinyl compounds, such as acrylicesters, acrylamides, vinylpyridine, vinyl chloride or vinylidenechloride, copolymers of dicyanoethylene and vinyl acetate as well asacrylonitrile block copolymers, fibres of polyurethanes, polypropylenefibres such as, cellulose triacetate and cellulose 21/2-acetate andespecially fibres of polyamides, such as nylon 6, nylon 6,6 or nylon 12,and of aromatic polyesters, such as those from terephthalic acid andethylene glycol or 1,4-dimethylcyclohexane, and copolymers ofterephthalic acid and isophthalic acid and ethylene glycol.

For dyeing in aqueous liquors, the water-insoluble dyestuffs areappropriately used in a finely divided form, and dyeing is carried outwith addition of dispersing agents, such as sulphite cellulose waste lyeor synthetic detergents, or of a combination of different wetting agentsand dispersing agents. As a rule it is advisable to convert thedyestuffs to be used, before dyeing, into a dyeing preparation whichcontains a dispersing agent and finely divided dyestuff in such a formthat on dilution of the dyestuff preparations with water a finedispersion is produced. Dyestuff preparations can be obtained in knownmanner, for example by grinding the dyestuff dry or wet with theaddition of textile auxiliaries, for example dispersants, during thegrinding process, or by grinding with solvents, such as sulpholane ordimethyl formamide.

In order to achieve intense dyeings on polyethylene terephthalatefibres, it proves advisable to add a swelling agent to the dyebath, orto carry out the dyeing process under pressure at temperatures above100°C, for example at 120°C. Suitable swelling agents are aromaticcarboxylic acids, for example salicylic acid, phenols, such as, forexample, o- or p-hydroxydiphenyl, aromatic halogen compounds, such aso-dichlorobenzene, or diphenyl.

For thermofixing the dyestuff, the padded polyester fabric is heated,appropriately after prior drying, for example in a warm stream of air,to temperatures of above 100°C, for example between 180° and 210°C, ortreated with superheated steam.

The dyeings obtained according to the present process can be subjectedto an after-treatment, for example by heating with an aqueous solutionof a non-ionic detergent.

Instead of being applied by impregnation, the compounds indicated can,according to the present process, also be applied by printing. For thispurpose, for example, a printing ink is used which contains the finelydisperse dyestuff in addition to the auxiliaries customary in printing,such as wetting agents and thickeners.

The present process yields powerful dyeings and prints of good fastnessproperties.

The new water-insoluble compounds can also be used for spin-dyeingpolyamides, polyesters and polyolefines. The polymer to be dyed isappropriately mixed in the form of powder, granules or chips, as aready-to-use spinning solution or in the fused state, with the dyestuff,which is introduced in the dry state or in the form of a dispersion orsolution in a solvent, which may be volatile. After homogeneousdistribution of the dyestuff in the solution or melt of the polymer, themixture is converted into fibres, yarns, monofilaments, films and thelike in a known manner, by casting, pressing or extrusion.

The new dyestuffs are also suitable for the multicolour printing oftextile materials consisting of hydrophobic, synthetic, organic fibreswhich are free from amino groups. because it is possible to achieve withthem resist effects on textile materials of such fibres. The procedureto be followed is that the material is padded with the new dyestuffswhich contain carboxyl groups, the padded material is dried, printedwith an alkaline printing paste containing fluorescent whitening agentswhich are free from carboxyl groups, white pigments or other colouringagents which are free from carboxyl groups, the fabric is fixed with theapplication of heat and subsequently the salt of the dyestuff containingcarboxyl groups is washed out of the printed areas.

As examples of synthetic fibres which may be dyed or printed in thismanner there may be mentioned: acrylic fibres, fibre of polyurethanes,polyepoxy based fibres or polyolefine fibres, for example polypropylene,in particular polypropylene modified with nickel or unmodifiedpolypropylene, and above all, fibres of aromatic polyesters, such asthose from terephthalic acid and ethylene glycol or1,4-dimethylolcyclohexane and from copolymers of terephthalic acid andisophthalic acid and ethylene glycol, also cellulose triacetate andcellulose 21/2-acetate. The fibres to be printed may not contain anyamino groups.

Also possible are blended fabrics of the above mentioned fibres andhydrophilic fibres, in particular cellulose fibres. Mention may also bemade of polyester/cotton blends.

The textile materials are as a rule woven fabrics, knitted fabrics, orother sheet materials such as non-wovens.

The new dyestuffs which contain carboxyl groups may be in the form ofsalts of volatile organic bases or ammonium salts.

As a rule, the padding liquor is aqueous. In addition to the dyestuff,it may also contain, if required, further auxiliaries, such as sodiumsalts of highly concentrated naphthalenesulphonic acid/formaldehyderesins, sulphite cellulose lye products, condensation products of highermolecular weight alcohols with ethylene oxide, polyglycol ethers offatty acid amides and alkylphenols, sulphosuccinic acid ester of Turkeyred oil. However, the padding liquor may also be a solution of thedyestuff.

After the textile material has been squeezed out to 20-200% by weight ofthe weight of the fibre, it is dried. The drying may be performed, forexample, with steam or preferably with a flow of warm air between 70°and150° C for 10 to 300 seconds.

Subsequently the fabric is printed with an alkaline printing paste whichcontains a heat-resistant alkaline compound, for example an alkalicarbonate, such as sodium carbonate or potassium carbonate or, aboveall, alkali hydroxides such as sodium or potassium hydroxide. The amountof alkali must be so gauged that the dyestuff present on the fibre isconverted with certainty into the alkali salt. If the resist remainswhite, the resist paste may contain white pigments such as titaniumdioxide or zinc oxide. In addition, the printing pastes contain theconventional additives, such as thickeners, for example gum arabic ormethyl cellulose.

To achieve two-colour prints, alkali-resistant dyestuffs, in particulardisperse dyestuffs, for example those listed in the Colour Index, areadded to the printing paste. These dyestuffs may not contain anycarboxyl groups.

Furthermore, it is also possible to introduce into the alkaline printingpaste fluorescent whitening agents which have affinity for the organicfabric (for example nylon and, above all, cellulose acetate andpolyester fabrics).

In addition to a disperse dyestuff which is free from carboxyl groups,the printing paste may also contain dyestuffs of other dyeingcategories, for example water-soluble or water-insoluble dyestuffs withfibre-reactive groups, such as di- or monochlorotriazine groups,chloroacetylamino groups and acrylic amide groups. The use ofwater-soluble, fibre reactive dyestuffs is of particular interest inthose cases where blended fabrics which contain cellulose are used assubstrate, in particular blended fabrics with polyester fibres. Ifprinting pastes are used with fibre-reactive dyestuffs, the alkalitreatment can be adapted to the modern methods for fixing reactivedyestuffs (alkali shock treatment).

In addition, fluorescent whitening agents are also suitable for theprinting. After the printing, the textile material can be dried withsteam or hot air or subjected direct to the fixing operation. The fixingof the dyestuff (or dyestuffs) on the textile material takes place withthe application of heat at 100°to 260° C, preferably at 150° to 230° C,but in the case of polymers with a low softening point at lowertemperatures, preferably with dry heat (thermosol process) in appliancessuitable for the purpose. It is also possible to use superheated steam.Prints on polypropylene are thermofixed at temperatures below 140° C.

After the fixing process the printed material is washed. The washing canbe carried out both in organic and, preferably, aqueous liquor. Theconventional surfactants or detergents are used for this purpose.

The following Examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated.

EXAMPLE I

3.8 Parts of sodium nitrite are dissolved in 70 parts of sulphuric acidmonohydrate. At approx. 10° C, 8.65 parts of 2-chloro-4-nitro-anilineare added and the mixture is stirred for 2 hours and poured on 300 partsof ice water. The resulting diazo solution is added at 0° to 5° C to asolution of 12.9 parts of 2-3'-methanesulphonamidophenyl aminopropionicacid in 100 parts of alcohol. The mixture is further stirred for 4hours. The precipitated dyestuff is filtered off and washed with wateruntil the washings show a neutral reaction. The resulting deystuff ofthe formula ##STR12## dyes polyester and cellulose acetate fibres in redshades having very good fastness properties.

The coupling component is obtained by reacting3-methanesulphonamidoaniline with acrylic acid.

EXAMPLE 2

1.5 Parts of sodium nitrite are sprinkled 18 parts of concentratedsulphuric acid 0°-15° C. The mixture is heated to 65° C until everythinghas dissolved, then cooled to 0° C, and 20 parts by volume of a mixtureof glacial acetic acid and propionic acid in the ratio 4:1 is addeddropwise. To the resulting solution is added dropwise a solution of 2.9parts of 2-amino-5-nitrothiazole in 20 parts by volume of a mixture ofglacial acetic acid and propionic acid (4:1) and the reaction mixture isfurther stirred for 3 hours at 0°-5° C. To this diazo solution are added1.5 parts of urea in small amounts. The so obtained diazo solution isadded at 0° C to 5° C to a solution of 5.76 parts of 2-3'-methanesulphonamido-6-methoxyphenyl aminopropionic acid in 70 partsof alochol. The mixture is further stirred for 10 hours and then dilutedwith water. The precipitated dyestuff is filtered off and washed withwater until the washings show a neutral reaction. The resulting dyestuffof the formula ##STR13## dyes polyester and cellulose fibres in blueshades having very good fastness properties.

EXAMPLE 3

3.54 Parts of 5-amino-3-phenyl-1,2,4-thiadiazole are dissolved in 20parts by volume of formic acid. At 0° to 5° C, 1.4 parts of sodiumnitrite are added and rinsed for 30 minutes. Then 0.05 parts ofsulphamic acid are added. Subsequently 5.44 parts of 2-3'-ethanesulphonamidophenyl aminopropionic acid are added and rinsedwith 3 parts by volume of formic acid. The mixture is slowly heated to60° C and stirred at this temperature for 2 hours. The paste is dilutedwith 300 parts of water, thoroughly stirred, filtered with suction andthe filter cake washed with water, to give the dyestuff of the formula##STR14## which dyes polyester fibres in red shades having very goodfastness properties.

If the diazo components listed in column I are coupled with the couplingcomponents listed in column II, dyestuffs are obtained which dyepolyester fibres in the shades indicated in column III.

    __________________________________________________________________________    I            II                   III                                         __________________________________________________________________________     1 2-cyano-4-nitro- aniline                                                                 ##STR15##           bluish red                                   2 4-amino-2,5-di-                                                                         "                    scarlet                                        chlorobenzene-sul-                                                            phonedimethylamide                                                          3 2-amino-6-nitro-                                                                        "                    red                                            benzthiazole                                                                4 3-amino-5-nitro-                                                                        "                    blue                                           2,1-benzisothiazole                                                         5 4-aminobenzoic acid benzyl ester                                                         ##STR16##           orange                                       6 2-amino-5-methyl- sulphonylthiazole                                                      ##STR17##           violet                                       7 4-nitro-2-tri- fluoromethylaniline                                                       ##STR18##           red                                          8 2,4-dicyanoaniline                                                                       ##STR19##           scarlet                                      9 4-nitroaniline                                                                           ##STR20##           "                                           10 2-bromo-4-nitro- aniline                                                                 ##STR21##           red.                                        11 2-amino-5-acetyl-                                                                       "                    violet                                         thiazole                                                                   12 2-methoxy-4- nitroaniline                                                                ##STR22##           "                                           13 2,6-dicyano-4-                                                                          "                    reddish blue                                   nitroaniline                                                               14 2-amino-6-methyl- sulphonyl-benz- thiazole                                               ##STR23##           red                                         15 2-methyl-4-nitro- aniline                                                                ##STR24##           scarlet                                     16 2-amino-6-dimethyl- amino-sulphonyl- benzthiazole                                        ##STR25##           red                                         17 2-nitro-4-phenyl- azoaniline                                                             ##STR26##           "                                           18 4-amino-3-chloro-                                                                       "                    scarlet                                        benzene-sulphon-                                                              amide                                                                      19 2-amino-6-cyano-                                                                        "                    red                                            benzthiazole                                                               20 2-amino-5-nitro- benzonic acid- methyl ester                                             ##STR27##           "                                           21 2-bromo-6-cyano-                                                                        "                    claret                                         4-nitroaniline                                                             22 2-chloro-4-nitro- aniline                                                                ##STR28##           red                                         23 5-amino-3-methoxy-                                                                      "                    "                                              carbonylethylthio-                                                            1,2,4-thiadiazole                                                          24 2,6-dichloro-4- nitroaniline                                                             ##STR29##           brown                                       25 4-amino-3-bromo-                                                                        "                    scarlet                                        benzene-sulphon-                                                              methylamide                                                                26 2-methylsulphonyl- 4-nitroaniline                                                        ##STR30##           bluish red                                  27 5-amino-3-methyl-                                                                       "                    red                                            sulphonyl-1,2,4-                                                              thiadiazole                                                                28 3-methyl-4-nitro- 5-amino-1,2-iso- thiazole                                              ##STR31##           violet                                      29 2-chloro-4,6-di-                                                                        "                    "                                              nitroaniline                                                               30 2-amino-5-cyano- thiazole                                                                ##STR32##           "                                           31 2-amino-5-phenyl- 1,3,4-thiadiazole                                                      ##STR33##           red                                         32 4-methylsulpho- nylaniline                                                               ##STR34##           red                                         33 2-amino-5-nitro- thiazole                                                                ##STR35##           blue                                        34 2-amino-5-acetyl-                                                                       "                    "                                              3-nitro-thiophene                                                          35 2,6-dicyano-4-nitro-                                                                    "                    "                                              aniline                                                                    36 5-amino-3-methyl-                                                                       "                    yellow                                         pyrazole                                                                   37 2-chloro-4-nitro- aniline                                                                ##STR36##           red                                         38 4-nitroaniline                                                                           ##STR37##                                                       39 2-amino-5-chloro- thiazole                                                               ##STR38##                                                       40 2,6-dichloro-4- nitroaniline                                                             ##STR39##           red                                         41 2-cyano-4-chloro- aniline                                                                ##STR40##           scarlet                                 

133 Parts of a 10% paste of the dyestuff obtained according to Example1, 200 parts of 2.5% sodium alginate solution and 1.5 parts by volume of40% acetic acid are made up to 1000 parts with water and polyesterfabric is padded with this liquor ans squeezed to 75% retention ofliquid. The fabric is dried for 1 minute at 120° C and a portion ofdried fabric is printed with white resist as follows: a paste of 20parts of sodium carbonate and 950 parts of 2.5% sodium alginate solutionis printed on the fabric in stripes. The fabric is thermofixed directlyfor 1 minute at 200° C and subsequently thoroughly washed with asolution containing the adduct of 9 mols of ethylene oxide with 1 mol ofnonylphenol. A fabric which is dyed red and with a white resist isobtained.

The printing paste may furthermore be treated with additives such asaluminum sec. butylate or m-nitrobenzene-sulphonate.

DYEING EXAMPLE

1 Part of the dyestuff obtained according to Example 1 is ground wetwith 2 parts of a 50% aqueous of the sodium salt ofdinaphthylmethane-disulphonic acid.

This dyestuff preparation is stirred with 40 parts of a 10% aqueoussolution of the sodium salt ofN-benzyl-μ-hepta-decyl-benzimidazole-disulphonic acid and 4 parts of a40% acetic acid solution are added. A dyebath of 4000 parts by volume isprepared therefrom by dilution with water.

100 Parts of a purified polyester fibre material is put into this bathat 50° C, the temperature is raised within half an hour to 120°-130° Cand dyeing is carried out for 1 hour at this temperature in a sealedvessel. The material is subsequently thoroughly rinsed. A powerful,pure, red dyeing is obtained.

I claim:
 1. A dyestuff of the formula ##STR41## in which D is phenyl, orphenyl substituted by chloro, bromo, nitro, trifluoromethyl, cyano,methoxy, methyl, sulfonamide, carbomethoxy, N-methylsulfonamide, ormethylsulphonyl,d is hydrogen, methoxy, ethoxy, chloro or methyl, R₁ ishydrogen, methyl, ethyl, cyanoethyl, hydroxyethyl, acetoxyethyl,methoxyethyl, benzyl, phenylethyl or butyl, R₂ is methylene, ethylene,propylene, isopropylene or phenylene, R is methyl, ethyl, propyl, butyl,phenyl, toluyl, dimethylamino or chloromethyl.
 2. An azo compound asclaimed in claim 1 of the formula ##STR42##
 3. An azo compound asclaimed in claim 1 of the formula ##STR43##